Process for dyeing cellulosic materials



United tates PROCESS FOR DYEING (ZELLULOSIC MATE WITH METALLIZABLE DRECTDYESTUFFS AND ANIONS OF A POLYPHOSPHORIQ ACE No Drawing. ApplicationDecember 12, 1952,

Serial No. 325,716

Claims priority, application Switzerland December 14, 1951 '14 Claims.(Cl. 8-42) This invention is based on the observation thatcellulose-containing materials can be dyed in an advantageous mannerwith metallizable direct dyestuffs, which form sparingly soluble metalcomplexes, by adding an agent yielding metal to a bath containing asmall quantity of non-metallized dyestuff, if there is used as an agentyielding metal an agent yielding nickel or copper and the metallizationis carried out in a neutral to alkaline medium in the presence of anionsof a polyphosphoric acid.

The dyestuffs used in the present process contain as metallizablegroups, for example, ortho-hydroxy-carboxylic acid (salicylic acid),ortho:ortho-dihydroxy-azoor ortho hydroxy ortho' carboxy azo-groupingsor 8-hydroxyquinoline radicals. There come into considerationexclusively those direct dyestuffs, that is to say, dyestufis suitablefor dyeing cellulose-containing materials by the usual direct dyeingmethods, of which the complex nickel or copper compounds prepared insubstance are so sparingly soluble in water themselves and in the formof their alkali salts that they cannot be used for dyeing by the usualmethods from an alkaline bath without special assistants. Thesemetallizable dyestuffs are advantageously used in the present process inthe form of their alkali salts. In some cases it is desirable todissolve the dyestufi with the addition of an alkali, for example, analkali carbonate or alkali hydroxide. A large excess of an alkalihydroxide is, however, preferably avoided as it may have adisadvantageous effect.

As agent yielding metal there come into consideration agents yieldingnickel and especially those yielding copper. The agent yielding metal isadded to the dyebath after or at the earliest simultaneously with theaddition of the compound providing anions of a polyphosphoric acid.

As agents yielding metal there may he used, for example, simplewater-soluble salts of nickel or copper, that is to say, those which donot contain the metal in complex union, such as nickel sulfate or coppersulfate. In this form of the process there are advantageously used ascompounds providing the anions of a polyphosphoric acid, alkali salts ofpolyphosphoric acids of the formula Hm+2PmO3m+1 in which m represents awhole number greater than one. Especially valuable are tetra-alkalipyrophosphates, for example, tetra-sodium pyrophosphate(NaePzOmlOI-lzO). These alkali pyrophosphates may be added to thedyebath at the outset, if desired, as an alkaline addition fordissolving the dyestufi (see above), or after the material to be dyedhas been entered in the dyebath, but at the, latest simultaneously withthe agent yielding metal.

A procedure that is especially advantageous in many cases is to use asthe agent yielding metal an alkali-nickel pyrophosphate or alkali-copperpyrophosphate, for example, sodium-copper pyrophosphate(3N84P207.CU2P207). As these compounds contain, in addition to the metalforming the complex, the residue of pyrophosphoric acid, the

' atent further addition of a phosphorus compound of the above kind isunnecessary.

In order to utilize the improvement in tinctorial properties broughtabout by the metallization of the dyestutf and to ensure alwaysproducing the same tint with the same dyestuff, there is used at leastthe theoretical quantity of the agent yielding metal required forcomplete metallization, and advantageously an amount in excess of thisquantity, for example, a total amount of up to twice the theoreticalquantity.

The quantity of the polyphosphoric acid ions in the dyebath has acertain influence on the result. In order to avoid the precipitation ofinsoluble copper compounds, the dyebath should contain at least 2 molsof pyrophosphate ions per gram-atom of copper (which corresponds to theconstitution of the sodium-copper pyrophosphate mentioned above).Provided that the excess of the agent yielding copper, calculated on thequantity of dyestutf used, is not inordinately high and amounts, forexample, to about 100 percent, it is desirable to make up the dyebath sothat it contains at most 8 mols of pyrophosphate ions per gram-atom ofcopper. A higher content of pyrophosphate ions may lead to incompletemetallization. From this fact, and from the observation that with alarge excess of pyrophosphate ions but with the same quantitative ratioof copper to pyrophosphate ions the incomplete metallization occurringunder the usual conditions can be considerably improved by a substantialincrease in the quantity of the agent yielding copper (and acorresponding increase in the amount of pyrophosphate), calculated onthe quantity of dyestufi it can be concluded that a kind of equilibriumreaction is involved.

In dyeing cellulose-containing materials with direct dyestufls thedyestuff, as is generally known, is not fixed on the goods to the extentof 100 percent, but a certain residue, which in some cases is quitesmall, always remains unused dissolved in the dyebath, although thedyeing process appears to be practically complete. At this stage of thedyeing process the metallization of the invention can generally bebrought about, that is to say, the agent yielding copper may be added.Whether it is possible without disadvantage, or may even be ofadvantage, to add the agent yielding metal beforehand, depends mainly onthe constitution of the-dyestuff and in part on the concentration of thebath. With some dyestuffs it is possible to add the agent yielding metalwhen the dyestuff is only partially fixed on the fiber. In the case of anumber of dyestuffs the dyeing may be carried out by adding the agentyielding metal at the outset, for example, it may be added to thedyebath before the material to be dyed is entered.

As has been briefly mentioned above, the dyestuffs are advantageouslyused in the form of their alkali salts. This applies also to theexamples of the process given above, although in the examples thedyestuffs, as is usual, are formulated in the form of the free acids.The dyestuffs can be made up to the desired strength with the usualagents each, for example, as sodium sulfate, sodium carbonate, urea,saccharose or dextrin. If this standardization to a predeterminedstrength is carried out with a sufiicient quantity of an alkalipyrophosphate, no further pyrophosphate need be added for dyeing, andthe metallization can be carried out merely by adding at the appropriatemoment a simple metal salt such, for example, as copper sulfate, withoutany other addition.

in other respects the dyeing carried out by one of the methods known fordirect dyeing dyestuffs at a raised temperature, for example, in aboiling bath or near the boiling point, and advantageously with theaddition of one of the usual salts, such as sodium sulfate.

In certain cases it may be of advantage to after-treat dyeings producedby the present process with agems which enhance their properties of wetfastness. In this connection there may be mentioned, for example,treatment with a reaction product of formaldehyde with a pompound suchas .cyana'mide, dicyanarnide, 'dicyandiamidine or melamine. There mayalso be mentioned after-treatment agents which are prepared withouttormaldehyde.

' the present processg it ishardly possible with the known methods toproduce useful dyeings when the agent yielding metal is added before thegreater part of the dyestuil V has been absorbed. The present processpossesses quite generally the surprising advantage that aliphatichydroxycarboxylic acids are not required, and the much more Ireadilyaccessible polyphosphates can be used with at least equal success. r

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated,.and therelationship between parts by weight and parts by volume being that ofthe kilogram to the liter:

. p Exa mple'v I 1 part of the dyestuif of the formula and 0.1 part ofsodium-hydroxide solution of 3.0 percent mixture is raised to the boil.A dyebath is prepared by diluting the resulting stock solution with 2900parts of 7 in parts by volume '10 parts of sodium-copper pyrophosphateare added to the dyebath. 100 parts of previously Wetted cotton are thenentered, and vthe bath temperature is raised to the boil: in the courseof A: hour. Boiling is carried on for hour, during which 2% parts ofcrystalline sodium sulfate are addedafter '10 minutes and a further 20parts thereof-after 20 minutes. At the end of this period the dyebath iswell exhausted. The dyeing is rinsed in the cold/centrifuged and dried.There is obtained a deep blue dyeing of good fastness to light andwashing.

A similar result is obtained if the sodium-copper pyrophosphate is addedduringrthe exhaustion of the dyebath or only at the end of theexhaustion.

By using, instead-of the aforesaid sodium-copper pyrophosphatesolutionythe same quantityof a'solutionof an equivalent quantity'of amixture of nickel sulfate and tetrasodium pyrophosphate.

Instead of dyeing with the dyestufi ofthe above formula OH HO H038 NH- S0311 V O O H V H O cotton may be dyed in the same manner with thefollowing dyestuffs:

Dyestufi of the formula Tint of dyeing 7 H038 .HNG' V Cu: Reddish grey.1 H0: NA Ni: Reddish grey.

7. SOsH 7 no=s BIN-G Cm Grey. 2.-.... H0 N== N=N N=N Ni: Navy blue.

doon no SOaH V V N\ H300 Hots NH-o C-NH SOsH CH3 I ll Cu: Reddlsh HO N=NN=N N N N=N N=N 0 g I p I Ni: Violet. oon on no. H V cm "000B 1 r NH:

' 'COdH r Cu: Brown. 4 no HO3S- NH-(fl) o-Nrr-G-u: 0H 7 3mm N N r asome";

Dyestufi of the formula ggg g OH HO OH HO Cu: Blue. HsN SOsH HOaS NH:Ni: Reddish blue.

OH H? OH HO N=N N=N e my 1H Ems NH iii iiii i (I JH: H: CH: CH: 6H 0EThe sodium-copper pyrophosphate is prepared as follows:

44.6 parts of crystalline sodium pyrophosphate are dissolved in 300parts of hot water, and the solution is added to a solution of 51 partsof crystalline copper sulfate (CuSO4.5HzO) in 200 parts of water. Thereis formed immediately a White precipitate of copper pyrophosphate, whichis filtered off and Washed with water.

The resulting copper pyrophosphate is introduced into a boiling solutionof 134 parts of crystalline sodium pyrophosphate in 150 parts of water,and boiling is continued until dissolution is complete. The deep blue,clear solution is evaporated in vacuo, and the easily water-solublesodium-copper pyrophosphate (3Na4P2O7.Cu2P2O7.3H2O) is obtained in theform of a pale powder.

Sodium nickel pyrophosphate is prepared in the same manner with thecorresponding equimolecular quantities of nickel sulfate and sodiumpyrophosphate.

Example 2 1 part of the dyestutf, obtained by reducing thenitrodisazo-dyestutf of the formula HOaS N=N OH with glucose in sodiumhydroxide solution, and 0.1 part of sodium hydroxide solution of 30percent strength are covered with 100 parts of water, and the mixture isboiled. By diluting the resulting stock solution with 2900'parts ofWater having a temperature of about 60 C. a dyebath is prepared.

100 parts of previously wetted cotton are entered and the bathtemperature is raised in the course of /2 hour to 100 C. Boiling iscontinued for hour, during which 20 parts of crystalline sodium sulfateare added after minutes and a further parts thereof after 20 minutes. Atthe end of this period there are added to the dyebath 20 parts by volumeof an aqueous solution containing in 100 parts by volume 10 parts ofsodium-copper pyrophosphate, and the treatment is continued for afurther 30 minutes. Thedyebath is well exhausted. The dyeing is rinsedin the cold, centrifuged and dried. There is obtained a grey dyeing ofgood fastness to light and Washing.

A similar result is obtained by adding the sodiumcopper pyrophosphate tothe dyebath at the beginning of the dyeing operation.

I SO10 copper pyrophosphate, the same quantity of a solution of 4.28parts of crystalline copper sulfate and 15.4 parts of By using, insteadof the aforesaid solution of sodiumcrystalline tetrasodium pyrophosphatein parts of water, the dyeing process gives a similar result.

A similar result is obtained by using, instead of sodiumcopperpyrophosphate, sodium nickel pyrophosphate or an equimolecular mixtureof nickel sulfate and tetrasodium pyrophosphate.

Example 3 p 1 part of the dyestufi of the formula CH3 CH: -OH (J-OH do IE do 00011 OOH 111K ITTH and 0.1 part of sodium hydroxide solution of 30percent strength are covered with parts of Water, and the mixture isboiled. A dyebath prepared by diluting the resulting stock solution with2900 parts of water having a temperature of about 60 C; i

100 parts of previously wetted cotton are entered and the temperature ofthe bath is raised to 100 C. in the course of A2 hour. Boiling iscontinued for hour, during which 20 parts of crystalline sodium sulfateare added after 10 minutes and a further 20 parts thereof after 20minutes. At the end of this period there are added to the dyebath 20parts by volume of an aqueous solution containing in 100 parts by volume10 parts of sodium-copper pyrophosphate, and the treatment is continuedfor 30 minutes. The dyebath is then Well exhausted. The dyeing is n'nsedin the cold, centrifuged and dried. There is obtained an orange-yellowdyeing of good fastness to light and washing.

By using instead of the aforesaid sodium-copper pyrophosphate solutionthe same quantity of a solution of 4.28 parts of crystalline coppersulfate and 15.4 parts of crystalline tetrasodium pyrophosphate in 90parts of Water, the dyeing process gives a similar result.

A similar result is obtained by using, instead of sodiumcopperpyrophosphate, sodium-nickel pyrophosphate or a mixture of solution ofequimolecular quantities of nickel sulfate and sodium pyrophosphate.

The dyestufi used in this example can be metallized, instead of with thederivatives of pyrophosphoric acid, with sodium-copper tripolyphosphate,hexasodinrn-copper tetrapolyphosphate and also with sodium-copperhexametaphosphate, or with mixtures-which yield these compounds, ofcopper sulfate -and sodium-tripolyphosphate, sodium tetrapolyphospliateor sodium hexametaphosphate.

Sodium-copper tripolyphosphate is prepared as follows:

3618 parts of anhydrous sodium tripolyphosphate ar dissolved -in 200parts -of hot water, end -the solution is equimolecular quantity' ofhexasodium tetrapolyphos- Sodium copperthexametaphosphate is preparedassfoladded to a solution of 25 parts of crystalline coppersul- 5 lows:V y t fate (CUSOILSHZO) in 100 parts of Water. There is y l g g f f limmediately formed a White precipitate of copper tripoly- 2 3 1 5 5 fi ii 6 unon phosphate, Which is filtered off and washed Withwa'ter. a e O aso H 1.011 S -g me Upper 7 Th 01 h sohatersoyobtainadfiis int-mducsdfate (CuS94.5I-I2O) 1n 160 parts or Water. The blue r c 2 2 O E 36 8 HM71, I 7 19 clear solution is then evaporated in vacuo, and the easily fa 01 ng P H 0 Pa 5 i fj s soluble sodium-copper hexametaphosphate isobtained as P yP P pafts of Waten and me mutate a blue tpowder. Insteadof the above mentioned sodium is boiled until dissolution is complete.The blue clear salts of thesaidjhosporioacid th cgn'esponding potassolution is evaporated in vacuo, and the easilysoluhle siumjcan bfiused. 7 pp tripolypho'sphate Obtained blue 15 Instead of using thedyestutfof the above formula, the powder. V following dyestuffs maybeused for dyeing cotton, linen By using, instead of sodiumtripolyphosphate an or rayon in the manner described in this example:'

7 Dyestufl of the formula Tint of dyeing V 9 H038. NH-CO-NH 7 $03K H Q Vassess.

l I e I V VYHOOCIJ CH3 HO 7 7 OH 7 OCH! COOH H300 HOaS- NH- S0311 00H, 7

H0O): (BB; 113) OH 7 H: OOH

oo'on olN OH=OH N-N CH=CH N----N c 5 r n e- 0 \O/ Q O v {Nl.Ora ge. 03HSOaH son: 802K 0 V 7 OH r a OH OOH SOVIVNHL V nooo. 7 7

I V v CuzBordeaux.

' on No,

' H018 N=N CO'OH on OK coon (EQOH 11038 7 NH 0311 00011 on 0H t r Cu:Reddish Ni l i ddish v (|3=N I N=c 1 :0 0H; $11, 0

1. Process for dyeing cellulosic materials with metallizable directdyestuffs, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnon-metallized dyestuff, which process comprises adding to the dyebathan agent yielding a metal having an atomic num her from 28 to 29 andcarrying out the metallization in a neutral to alkaline medium in thepresence of anions of a polyphosphoric acid and in the absence ofamines.

2. Process for dyeing cellulosic materials with metallizable directdyestuffs, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnon-metallized dyestufl, which process comprises adding to the dyebathan agent yielding a metal having an atomic number from 28 to 29 andcarrying out the metallization in a neutral to alkaline medium in thepresence of anions of a polyphosphoric'acid of the formula in which mrepresents a Whole number greater than 1 and in the absence of amines.

3. Process for dyeing cellulosic materials with metallizable directdyestufis,, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnon-metallized dyestufi, which process comprises adding to the dyebathan agent yielding a metal having an atomic number from 28 to 29 andcarrying out the metallization in a neutral to alkaline medium in thepresence of anions of pyrophosphoric acid and in the absence of amines.

4. Process for dyeing cellulosic materials with metallizable directdyestufis, which form sparingly soluble metal complexes, by adding anagent yielding metal toa bath containing at least a small quantity ofnon-' metallized dyestufif, which process comprises adding to r thedyebath an agent yielding ametal having an atomic number from 28 to 29and carrying out the metallization in a neutral to alkaline medium inthe presence of anions of hexametaphosphoric acid and in the absence ofamines.

5. Process for dyeing cellulosic materials with metallizable directdyestuffs, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnonmetallized dyestufi, which process comprises adding to the dyebath anagent yielding a metal having an atomic number from 28 to 29 andcarrying out the metallization H035 HOC N=N N: N=N

00 on no in a neutral to alkaline medium and in the presence of anionsof pyrophosphoric acid provided by the addition of an alkalipyrophosphate and in the absence of amines.

6. Process for dyeing cellulosic materials with metallizable directdyestufis, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnonthe dyebath an alkali-Me pyrophosphate, Merepresent ing a metalhaving an atomic number from 28 to 29 and carrying out the metallizationin a neutral to alkaline medium and in the absence of amines.

7. Process for dyeing cellulosic materials with metallizable directdyestufis, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnon metallized dyestufl", which process comprises adding to the dyebathan agent yielding copper and carrying out the metallization in a neutralto alkaline medium and in the presence of anions of pyrophosphoric acidprovided by the addition of an alkali pyrophosphate and in the absenceof amines.

8. Process for dyeing cellulosic materials with metallizable directdyestuffs, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnonmetallized dyestuif, which process comprises adding to the dyebath analkali-copper pyrophosphate and carrying out the metallization in aneutral to alkaline medium and in the absence of amines.

9. Process for dyeing cellulosic materials with metallizable directdyestuffs, which form sparingly soluble metal'complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnonmetallized dyestufi, which process comprises adding to the dyebath analkali-nickel pyrophosphate and carrying out the metallization in aneutral to alkaline medium and in the absence of amines.

10. Process for dyeing cellulosic materials with metallizable directdyestuffs, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnonmetallized dyestufii, which process comprises adding to the dyebathwherein the dyestufi of the formula COOH 7 SOaH is for the most partfixed on the material to be dyed,

and the dissolved dyestufi of the formula and carrying out themetallization in a neutral to alkaline medium and in the absence ofamines.

12. Process for dyeing cellulosic materials with metallizable directdyestufls, which form sparingly soluble metal complexes, by adding anagent yielding metal to a bath containing at least a small quantity ofnonmetallized dyestuff, which process comprises adding metallizeddyestuif, which process comprises adding to 75 sodium-copperpyrophosphate to the dyebath before the material to be dyed is enteredWhich dyebath contains theidissolyed dyestuft-pt the formula V andcarrying ontjthe metalliz ati onin a neutral to alkaline um-and n t e bsce of a ines. j 13. {Process for dyeing cellnlosic materialswithvmetallizable direct dyestuffs, which form sparingly soluble metalpomplexes, by addinganage'ntyielding metal to a bath containing atleasta small qnantity of non-- metalli zed,dyestuif, which4process comprisesadding 7 sodium-popper pyrophosphate to thedyebath before the S OzNH:

material to be'dyedis entered, which dyebath contains thedissolveddyestufl? of the formula 12 and carrying out the metalli zation in a neutral to alkaline medium and in the absence of amines.

14. Process for dyeing cellulosic materials with metallizable directdyestuffs, which form sparingly soluble metal complexes, by adding anagent yieldin'grmetal to a bath containing at least a small quantity of"non-v metallized dyestufi; which process comprises addingvsodium-nickel pyr-ophospha te to the dyebatli before the material to bedyed is entered, which dyebathcontains the dissolved dyestufi of theformul'a END 1 and carrying out the. metallization in a neutral toalkaline medium and in the absence of amines;

References Cited in the file of this patent UNITED STATES PATENTS y 7OTHER REFERENCES v Ind, and-Eng. Chem., for November 1951, p. 5A(advertisement) American Dyestufir Reporter, fol-January 28, 1935;

pp, 40 to .47.

1. PROCESS FOR DYEING CELLULOSE MATERIALS WITH METALLIZABLE DIRECTDYESTUFFS, WHICH FORM SPARINGLY SOLUBLE METAL COMPLEXES, BY ADDING ANAGENT YIELDING METAL TO A BATH CONTAINING AT LEAST A SMALL QUANTITY OFNON-METALLIZED DYESTUFF, WHICH PROCESS COMPRISES ADDING TO THE DYEBATHAN AGENT YIELDING A METAL HAVING AN ATOMIC NUMBER FROM 28 TO 29 ANDCARRYING OUT THE METALLIZATION IN A NEUTRAL TO ALKALINE MEDIUM IN THEPRESENCE OF ANIONS OF A POLYPHOSPHORIC ACID AND IN THE ABSENCE OFAMINES.